(5R,6R)-5-(4-methylphenyl)-6-(phenylthio)-5,6,7,-8-tetrahydronaphtho[2,3-d]-1,3-dioxole | 1430205-69-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (5R,6R)-5-(4-methylphenyl)-6-(phenylthio)-5,6,7,-8-tetrahydronaphtho[2,3-d]-1,3-dioxole
• 英文别名: (5R,6R)-5-(4-methylphenyl)-6-phenylsulfanyl-5,6,7,8-tetrahydrobenzo[f][1,3]benzodioxole
• CAS: 1430205-69-8
• 化学式: C₂₄H₂₂O₂S
• 分子量: 374.503
• InChiKey: JENNLBBCIUCREU-DNQXCXABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  43.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5R,6R)-5-(4-methylphenyl)-6-(phenylthio)-5,6,7,-8-tetrahydronaphtho[2,3-d]-1,3-dioxole 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以94%的产率得到(5R,6R)-5-(4-methylphenyl)-6-(phenylsulfonyl)-5,6,7,8-tetrahydronaphtho[2,3-d]-1,3-dioxole
  参考文献：
  名称：

  Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins

  摘要：

  The first catalytic, enantioselective carbosulfenylation of alkenes with an aromatic nucleophile is described, using a BINAM-based selenophosphoramide catalyst. E-Alkyl- and aryl-substituted alkenes afforded tetrahydronaphthalenes with complete diastereospecificity, and generally high enantiomeric ratios.

  DOI：

  10.1021/ja401867b
• 作为产物：
  描述：

  N-(苯硫基)邻苯二甲酰亚胺 、 在 甲烷磺酸 、 (S)-4-(diisopropylamino)-3,5-dimethyl-4,5-dihydro-3H-dinaphtho[2,1-d:1’,2’-f][1,3,2]diazaphosphepine-4-selenide 作用下， 以 氘代氯仿 为溶剂， 反应 48.0h， 生成 (5R,6R)-5-(4-methylphenyl)-6-(phenylthio)-5,6,7,-8-tetrahydronaphtho[2,3-d]-1,3-dioxole 、
  参考文献：
  名称：

  Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. Mechanistic Aspects: A Remarkable Case of Negative Catalysis

  摘要：

  In the course of developing an enantioselective, Lewis base/Bronsted acid co-catalyzed carbosulfenylation of alkenes, a seemingly impossible conundrum arose: How could a catalyst inhibit a stoichiometric reaction? Despite the observation of very good enantioselectivities, the rate of the uncatalyzed reaction (i.e., no Lewis base) was found to be comparable to or slightly faster than that of the catalyzed process. A combination of detailed kinetic and spectroscopic studies revealed that the answer is not the direct involvement of the Lewis base catalyst, but rather the secondary consequences of its conversion to the catalytically active sulfenylating agent. Generation of the chiral sulfenylating species is accompanied by the formation of equimolar amounts of sulfonate ion and phthalimide which serve to buffer the remaining Bronsted acid and thus inhibit the racemic background reaction. Thus, the actual background reaction operative under catalytic conditions is not well mimicked by simply removing the catalyst.

  DOI：

  10.1021/ja413270h

文献信息

• Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. Preparative and Stereochemical Aspects
  作者：Scott E. Denmark、Alex Jaunet

  DOI：10.1021/jo4023765

  日期：2014.1.3

  The first catalytic, enantioselective, intramolecular carbosulfenylation of isolated alkenes with aromatic nucleophiles is described. The combination of N-phenylsulfenylphthalimide, a chiral selenophosphoramide derived from BINAM, and ethanesulfonic acid as a cocatalytic Brønsted acid induced an efficient and selective cyclofunctionalization of various alkenes (aliphatic and aromatic) tethered to a

  描述了分离的烯烃与芳香亲核试剂的第一次催化、对映选择性、分子内碳磺基化。的组合Ñ -phenylsulfenylphthalimide，从BINAM衍生的手性selenophosphorAMide和乙酸作为助催化布朗斯台德酸而引起的各种烯烃（脂族和芳族的）的有效和选择性cyclofunctionalization拴3,4-亚甲二氧苯基环。在这些条件下，6-苯硫基-5,6,7,8-四氢萘以良好的产率 (50–92%) 和高对映选择性 (71:29–97:3 er) 非对映特异性地形成。E-烯烃的反应速度比Z快得多，选择性也高得多-烯烃，而富电子烯烃反应更快，但选择性与电子中性烯烃和缺电子烯烃相当。布朗斯台德酸在影响可重现的对映选择性方面发挥了关键作用。提出了对映选择性起源的模型以及速率和选择性对烯烃结构的依赖性，以及与单活化芳烃亲核试剂反应的位点选择性的基本原理。